JP2008056533A - Quartz glass and method of manufacturing the same - Google Patents

Quartz glass and method of manufacturing the same Download PDF

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JP2008056533A
JP2008056533A JP2006236178A JP2006236178A JP2008056533A JP 2008056533 A JP2008056533 A JP 2008056533A JP 2006236178 A JP2006236178 A JP 2006236178A JP 2006236178 A JP2006236178 A JP 2006236178A JP 2008056533 A JP2008056533 A JP 2008056533A
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quartz glass
quartz
mixed
powder
producing
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Tatsuhiro Sato
龍弘 佐藤
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Shin Etsu Quartz Products Co Ltd
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Shin Etsu Quartz Products Co Ltd
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Priority to JP2006236178A priority Critical patent/JP2008056533A/en
Priority to DE602007005556T priority patent/DE602007005556D1/en
Priority to EP07114836A priority patent/EP1894896B1/en
Priority to US11/897,406 priority patent/US7905932B2/en
Publication of JP2008056533A publication Critical patent/JP2008056533A/en
Priority to US13/023,262 priority patent/US8156761B2/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • C03B19/063—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction by hot-pressing powders
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    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
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    • C03C3/00—Glass compositions
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    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/08—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant
    • C03B2201/12—Doped silica-based glasses doped with boron or fluorine or other refractive index decreasing dopant doped with fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
    • C03B2201/24—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with nitrogen, e.g. silicon oxy-nitride glasses
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2201/00—Type of glass produced
    • C03B2201/06—Doped silica-based glasses
    • C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
    • C03B2201/34—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with rare earth metals, i.e. with Sc, Y or lanthanides, e.g. for laser-amplifiers
    • C03B2201/36—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with rare earth metals, i.e. with Sc, Y or lanthanides, e.g. for laser-amplifiers doped with rare earth metals and aluminium, e.g. Er-Al co-doped
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/08—Doped silica-based glasses containing boron or halide
    • C03C2201/12—Doped silica-based glasses containing boron or halide containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/20—Doped silica-based glasses containing non-metals other than boron or halide
    • C03C2201/23—Doped silica-based glasses containing non-metals other than boron or halide containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/20—Doped silica-based glasses containing non-metals other than boron or halide
    • C03C2201/24—Doped silica-based glasses containing non-metals other than boron or halide containing nitrogen, e.g. silicon oxy-nitride glasses
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/20—Doped silica-based glasses containing non-metals other than boron or halide
    • C03C2201/26—Doped silica-based glasses containing non-metals other than boron or halide containing carbon
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/32—Doped silica-based glasses containing metals containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/3411—Yttrium
    • C—CHEMISTRY; METALLURGY
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/3435—Neodymium
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    • C03C2201/00—Glass compositions
    • C03C2201/06—Doped silica-based glasses
    • C03C2201/30—Doped silica-based glasses containing metals
    • C03C2201/34—Doped silica-based glasses containing metals containing rare earth metals
    • C03C2201/36—Doped silica-based glasses containing metals containing rare earth metals containing rare earth metals and aluminium, e.g. Er-Al co-doped

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  • Manufacturing & Machinery (AREA)
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  • Glass Melting And Manufacturing (AREA)
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Abstract

<P>PROBLEM TO BE SOLVED: To provide quartz glass used for semiconductor manufacture and having excellent corrosion resistance to plasma, a quartz glass tool, a method of manufacturing the quartz glass, mixed quartz powder suitably used for the manufacture of the quartz glass and a method of manufacturing the mixed quartz powder. <P>SOLUTION: The quartz glass contains 0.1 to 20 mass% in total of two or more of dope elements. The dope element contains one or more of first elements selected from the group composed of N, C and F and one or more of second elements selected from the group composed of Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, lanthanoids, and actinoids. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、半導体製造に用いられかつプラズマ耐食性に優れた石英ガラス、該石英ガラスを含む石英ガラス治具、該石英ガラスの製造方法、該石英ガラスの製造に用いられる混合石英粉、並びに該混合石英粉の製造方法に関する。   The present invention relates to quartz glass used for semiconductor production and excellent in plasma corrosion resistance, a quartz glass jig containing the quartz glass, a method for producing the quartz glass, a mixed quartz powder used for producing the quartz glass, and the mixture The present invention relates to a method for producing quartz powder.

半導体の製造、例えば半導体ウェーハの製造においては、近年における大口径化の増大とともにエッチング工程などにおいてプラズマ反応装置を用いることによって処理効率を向上させることが行われている。例えば、半導体ウェーハのエッチング工程においては、プラズマガス、例えばフッ素（Ｆ）系プラズマガスを用いたエッチング処理が行われる。   In the manufacture of semiconductors, for example, the manufacture of semiconductor wafers, the processing efficiency is improved by using a plasma reactor in an etching process or the like as the diameter increases in recent years. For example, in a semiconductor wafer etching process, an etching process using a plasma gas, for example, a fluorine (F) plasma gas is performed.

しかし、従来の石英ガラスを、例えばＦ系プラズマガス雰囲気中に置くと、石英ガラス表面でＳｉＯ2とＦ系プラズマガスが反応して、ＳｉＦ4が生成し、これは、沸点が−８６℃である為容易に昇華し、石英ガラスは多量に腐食して、減肉したり面荒れが進行し、Ｆ系プラズマガス雰囲気では、治具としての使用に適さなかった。 However, when conventional quartz glass is placed in, for example, an F-based plasma gas atmosphere, SiO 2 and F-based plasma gas react on the quartz glass surface to produce SiF 4 , which has a boiling point of −86 ° C. Therefore, it sublimated easily, and quartz glass was corroded in large quantities, resulting in thinning and surface roughness, and was not suitable for use as a jig in an F-based plasma gas atmosphere.

このように、従来の石英ガラスは、半導体製造におけるプラズマ反応、特にＦ系プラズマガスを用いるエッチング処理に対しては耐食性、即ちプラズマ耐食性に大きな問題が生じていた。そこで、アルミニウムやアルミニウム化合物を石英ガラス部材表面に被覆してプラズマ耐食性を向上させる提案（特許文献１〜３）や、石英ガラスに対してアルミニウムを含有せしめることによってプラズマ耐食性を向上させたプラズマ耐食性ガラスについての提案がなされている（特許文献４）。   As described above, the conventional quartz glass has a large problem in the corrosion resistance, that is, the plasma corrosion resistance, with respect to the plasma reaction in the semiconductor manufacturing, particularly the etching process using the F-based plasma gas. Therefore, proposals for improving plasma corrosion resistance by coating the surface of quartz glass member with aluminum or aluminum compound (Patent Documents 1 to 3), and plasma corrosion resistance glass with improved plasma corrosion resistance by containing aluminum in quartz glass. Has been proposed (Patent Document 4).

この手法によると、石英ガラス粉にアルミナ粉を５ｗｔ％混合したものを、真空下で加熱溶融して石英ガラスを作成し、プラズマ耐食性を調査した。すると、全くドープしていない石英ガラス部材に比べてエッチング速度が４０％〜５０％低下する。
というのも、Ｆ系プラズマガスと反応して生成するＡｌＦ3の沸点は１２９０℃で、ＳｉＦ4よりもはるかに高温である為、ＳｉＦ4部分が多量に腐食する一方で、ＡｌＦ3部分は表面における昇華が少なく、エッチング量の差違が拡大する為と推定される。
特開平９−９５７７１号公報 特開平９−９５７７２号公報 特開平１０−１３９４８０号公報 特開平１１−２２８１７２号公報 According to this method, quartz glass powder mixed with 5 wt% of alumina powder was heated and melted under vacuum to prepare quartz glass, and the plasma corrosion resistance was investigated. Then, the etching rate is reduced by 40% to 50% compared to a quartz glass member that is not doped at all.
Because in F-based boiling point 1290 ° C. of AlF 3 that reacts with the plasma gas, since it is much hotter than the SiF 4, while the SiF 4 portion is a large amount of corrosion, AlF 3 portion surface It is estimated that the difference in etching amount is widened because of less sublimation.
JP-A-9-95771 JP-A-9-95777 Japanese Patent Laid-Open No. 10-139480 JP-A-11-228172

しかし、これらの部材のエッチング速度は、セラミック治具などに比較してまだまだ大きく、さらなるエッチング速度の低下が、強く求められた。
本発明は、半導体製造に用いられかつプラズマ耐食性に優れた石英ガラス、石英ガラス治具、該石英ガラスの製造方法、該石英ガラスの製造に好適に用いられる混合石英粉、並びに該混合石英粉の製造方法を提供することを目的とする。 However, the etching rate of these members is still larger than that of a ceramic jig or the like, and further reduction of the etching rate has been strongly demanded.
The present invention relates to a quartz glass, a quartz glass jig, a method for producing the quartz glass, a mixed quartz powder suitably used for the production of the quartz glass, and a mixed quartz powder used in semiconductor production and having excellent plasma corrosion resistance. An object is to provide a manufacturing method.

上記課題を解決するため、本発明の石英ガラスは、２種以上のドープ元素を併せて０．１〜２０質量％含有する石英ガラスであって、前記ドープ元素が、Ｎ、Ｃ及びＦからなる群から選択される１種以上の第１の元素と、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、ランタノイド及びアクチノイドからなる群から選択される１種以上の第２の元素とを含むことを特徴とする。
前記第１の元素の総和（Ｍ１）と、前記第２の元素の総和（Ｍ２）の配合比が、原子数比率で（Ｍ１）／（Ｍ２）＝０．１〜２０であることが好ましい。 In order to solve the above problems, the quartz glass of the present invention is a quartz glass containing 0.1 to 20% by mass of two or more kinds of doping elements, and the doping elements are composed of N, C and F. One or more first elements selected from the group and one or more second elements selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, lanthanoids and actinoids And an element.
The compounding ratio of the sum of the first elements (M1) and the sum of the second elements (M2) is preferably (M1) / (M2) = 0.1-20 in terms of the number of atoms.

本発明の石英ガラスにおいて、前記ドープ元素が、さらにＡｌを含むことが好適である。
前記第１の元素及びＡｌの総和（Ｍ１＋Ａｌ）と、前記第２の元素の総和（Ｍ２）の配合比が、原子数比率で（Ｍ１＋Ａｌ）／（Ｍ２）＝０．１〜２０であることが好ましい。 In the quartz glass of the present invention, it is preferable that the doping element further contains Al.
The compounding ratio of the sum of the first element and Al (M1 + Al) and the sum of the second element (M2) is an atomic ratio of (M1 + Al) / (M2) = 0.1-20. preferable.

本発明の石英ガラス治具は、表面から少なくとも１ｍｍ深さまでの厚さに本発明の石英ガラスからなる層を形成したことを特徴とする。   The quartz glass jig of the present invention is characterized in that a layer made of the quartz glass of the present invention is formed to a thickness of at least 1 mm from the surface.

本発明の混合石英粉は、２種以上のドープ元素を併せて０．１〜２０質量％含有する混合石英粉であって、前記ドープ元素が、Ｎ、Ｃ及びＦからなる群から選択される１種以上の第１の元素と、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、ランタノイド及びアクチノイドからなる群から選択される１種以上の第２の元素とを含むことを特徴とする。
前記第１の元素の総和（Ｍ１）と、前記第２の元素の総和（Ｍ２）の配合比が、原子数比率で（Ｍ１）／（Ｍ２）＝０．１〜２０であることが好ましい。 The mixed quartz powder of the present invention is a mixed quartz powder containing 0.1 to 20% by mass of two or more kinds of doping elements, wherein the doping elements are selected from the group consisting of N, C and F. Including one or more first elements and one or more second elements selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, lanthanoids and actinoids It is characterized by.
The compounding ratio of the sum of the first elements (M1) and the sum of the second elements (M2) is preferably (M1) / (M2) = 0.1-20 in terms of the number of atoms.

本発明の混合石英粉において、前記ドープ元素が、さらにＡｌを含むことが好ましい。
前記第１の元素及びＡｌの総和（Ｍ１＋Ａｌ）と、前記第２の元素の総和（Ｍ２）の配合比が、原子数比率で（Ｍ１＋Ａｌ）／（Ｍ２）＝０．１〜２０であることが好適である。 In the mixed quartz powder of the present invention, it is preferable that the dope element further contains Al.
The compounding ratio of the sum of the first element and Al (M1 + Al) and the sum of the second element (M2) is an atomic ratio of (M1 + Al) / (M2) = 0.1-20. Is preferred.

本発明の混合石英粉の製造方法の第１の態様は、前記ドープ元素を各々又は併せて含有する１種又は２種以上の揮発性物質の気体を、水酸基を有する石英粉中に拡散させて、２００℃〜１１００℃の温度領域で加熱処理することを特徴とする。該方法により、本発明の混合石英粉が好適に製造される。   In the first aspect of the method for producing a mixed quartz powder of the present invention, a gas of one or more volatile substances each containing or in combination with the doping element is diffused in the quartz powder having a hydroxyl group. The heat treatment is performed in a temperature range of 200 ° C. to 1100 ° C. By this method, the mixed quartz powder of the present invention is suitably produced.

本発明の混合石英粉の製造方法の第２の態様は、前記ドープ元素及び石英粉を含む溶液を乾燥することを特徴とする。該方法により、本発明の混合石英粉が好適に製造される。   A second aspect of the method for producing a mixed quartz powder of the present invention is characterized in that the solution containing the dope element and the quartz powder is dried. By this method, the mixed quartz powder of the present invention is suitably produced.

本発明の石英ガラスの製造方法の第１の態様は、ベルヌイ法で石英粉からプラズマ耐食性に優れた石英ガラスを作成する方法であって、前記石英粉が前述した本発明の混合石英粉であり、該混合石英粉を加熱溶融落下させ石英ガラスインゴットを作成する際、該石英ガラスインゴット表面温度を、１８００℃以上に加熱することを特徴とする。該方法により、本発明の石英ガラスが好適に製造される。
加熱雰囲気エリアに還元性ガスが供給され、供給される水素／酸素の比率が２．５以上であることが好ましい。また、加熱雰囲気エリアにＮまたはＣを含むガスが供給されることが好適である。 A first aspect of the method for producing quartz glass of the present invention is a method for producing quartz glass having excellent plasma corrosion resistance from quartz powder by the Bernoulli method, wherein the quartz powder is the mixed quartz powder of the present invention described above. The quartz glass ingot surface temperature is heated to 1800 ° C. or higher when producing the quartz glass ingot by melting and dropping the mixed quartz powder. By this method, the quartz glass of the present invention is preferably produced.
It is preferable that a reducing gas is supplied to the heating atmosphere area, and the supplied hydrogen / oxygen ratio is 2.5 or more. In addition, it is preferable that a gas containing N or C is supplied to the heating atmosphere area.

本発明の石英ガラスの製造方法の第２の態様は、前述した本発明の混合石英粉を、成型鋳型に詰めて、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で１３００℃以上に加熱溶融して、石英ガラスインゴットを作成することを特徴とする。   In the second aspect of the method for producing quartz glass of the present invention, the mixed quartz powder of the present invention described above is packed in a mold and heated to 1300 ° C. or higher under reduced pressure or in a reducing or inert gas atmosphere. It is characterized by melting to produce a quartz glass ingot.

本発明の石英ガラスの製造方法の第３の態様は、前述した本発明の混合石英粉を、石英管の中に詰めて、管内を減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気にして、管外面より１３００℃以上に加熱溶融して、石英ガラスインゴットを作成することを特徴とする。   In the third aspect of the method for producing quartz glass of the present invention, the mixed quartz powder of the present invention described above is packed in a quartz tube, and the inside of the tube is under reduced pressure or a reducing or inert gas atmosphere, A quartz glass ingot is produced by heating and melting to 1300 ° C. or more from the outer surface of the tube.

本発明の石英ガラスの製造方法の第４の態様は、前記２種以上のドープ元素を各々又は併せて含有する１種又は２種以上の揮発性物質の気体を、水酸基を有する石英多孔質体に拡散させて、２００℃〜１１００℃の温度領域で加熱処理したのち、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で１３００℃以上に加熱溶融して、石英ガラスインゴットを作成することを特徴とする。   According to a fourth aspect of the method for producing quartz glass of the present invention, a quartz porous body having a hydroxyl group is used as a gas of one or two or more volatile substances each containing the two or more kinds of doping elements or in combination. And then heat-treating in a temperature range of 200 ° C. to 1100 ° C., and then heat-melting to 1300 ° C. or higher under reduced pressure or in a reducing or inert gas atmosphere to produce a quartz glass ingot. Features.

本発明の石英ガラスの製造方法の第５の態様は、前記ドープ元素を含む溶液中に、石英多孔質体を漬し、乾燥後、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で１３００℃以上の温度で加熱溶融して、石英ガラスインゴットを作成することを特徴とする。   According to a fifth aspect of the method for producing quartz glass of the present invention, a porous porous body is immersed in a solution containing the doping element, dried, and then dried under reduced pressure or in a reducing atmosphere or an inert gas atmosphere. A quartz glass ingot is produced by heating and melting at a temperature of at least ° C.

本発明の石英ガラスの製造方法の第６の態様は、前記ドープ元素及び石英粉を含む溶液を乾燥し、多孔質体を作成し、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で１３００℃以上の温度で加熱溶融して、石英ガラスインゴットを作成することを特徴とする。   According to a sixth aspect of the method for producing quartz glass of the present invention, the solution containing the dope element and quartz powder is dried to prepare a porous body, and 1300 in a reduced or inert gas atmosphere under reduced pressure. A quartz glass ingot is produced by heating and melting at a temperature of at least ° C.

本発明の石英ガラスの製造方法の第２〜第６の態様において、前記加熱溶融時の圧力が、２ｋｇ／ｃｍ2以上であることが好適である。 In the second to sixth embodiments of the method for producing quartz glass of the present invention, it is preferable that the pressure at the time of heating and melting is 2 kg / cm 2 or more.

本発明の石英ガラスの製造方法において、前記作成された石英ガラスインゴットを２ｋｇ／ｃｍ2以上の圧力下の不活性ガス雰囲気中にて１５００℃以上の温度で再度加熱成型することが好ましい。該加熱成型処理により、ガラスインゴット中に残留する泡、クラックを除去することができる。 In the method for producing quartz glass of the present invention, it is preferable that the produced quartz glass ingot is heat-molded again at a temperature of 1500 ° C. or higher in an inert gas atmosphere under a pressure of 2 kg / cm 2 or higher. By the heat molding treatment, bubbles and cracks remaining in the glass ingot can be removed.

本発明の石英ガラス及び石英ガラス治具は、半導体製造に用いられるプラズマ反応用治具材料として、プラズマ耐食性、特にＦ系プラズマガスに対する耐食性に優れているという効果を有している。本発明方法は、プラズマ耐食性に優れた石英ガラスを効率よく製造できるという利点を有している。本発明の混合石英粉は本発明の石英ガラスの材料として特に好ましい。本発明の混合石英粉の製造方法により、本発明の混合石英粉を簡便に得ることができる。   The quartz glass and quartz glass jig of the present invention have an effect of being excellent in plasma corrosion resistance, particularly corrosion resistance against F-based plasma gas, as a plasma reaction jig material used in semiconductor manufacturing. The method of the present invention has an advantage that quartz glass excellent in plasma corrosion resistance can be produced efficiently. The mixed quartz powder of the present invention is particularly preferable as a material for the quartz glass of the present invention. The mixed quartz powder of the present invention can be easily obtained by the mixed quartz powder manufacturing method of the present invention.

以下に本発明の実施の形態を説明するが、これらは例示的に示されるもので、本発明の技術思想から逸脱しない限り種々の変形が可能なことはいうまでもない。   Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

本発明の石英ガラスは、２種以上のドープ元素を併せて０．１〜２０質量％、より好ましくは１．０〜１７質量％含有する石英ガラスであって、前記ドープ元素として、Ｎ、Ｃ及びＦからなる群から選択される１種以上の第１の元素と、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、ランタノイド及びアクチノイドからなる群から選択される１種以上の第２の元素とを含むものである。   The quartz glass of the present invention is a quartz glass containing 0.1 to 20% by mass, more preferably 1.0 to 17% by mass of two or more kinds of doping elements, and N, C as the doping elements And one or more first elements selected from the group consisting of F and F, and one or more selected from the group consisting of Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, lanthanoids and actinoids And the second element.

前記第１の元素は、Ｆ系プラズマガスとの化学的エッチング反応を抑制し、全体のエッチング速度を低下させることができる。
さらに、前記第２の元素は、Ａｌに比べて弗化物となったときの沸点が高く、エッチング速度をより低下させることができる。例えばＮｄＦ3の沸点は２３２７℃であるので、プラズマ耐食性を調査すると、全くドープしていない石英ガラス部材に比べてエッチング速度を低下させることができる。結果として、エッチング速度は、７０％〜９５％低下した。 The first element can suppress the chemical etching reaction with the F-based plasma gas and reduce the overall etching rate.
Further, the second element has a higher boiling point when it becomes a fluoride than Al, and can further reduce the etching rate. For example, since the boiling point of NdF 3 is 2327 ° C., when the plasma corrosion resistance is investigated, the etching rate can be reduced as compared with a quartz glass member that is not doped at all. As a result, the etching rate was reduced by 70% to 95%.

また、前記第１の元素は、前記第２の元素と共存することで、電気的に安定し、原子状態での分散がよくなり、縮合して白色異物を形成することがなくなり、クラック発生からのパーティクル発生が抑制されるとともに、石英ガラス内でより安定化して、エッチング速度をより低下させることができる。さらに、前記第１の元素は、半導体製造工程では最も影響の小さい元素であるので、好適である。   Further, the first element coexists with the second element, so that the first element is electrically stable, the dispersion in the atomic state is improved, the condensation does not form a white foreign substance, and the generation of cracks is prevented. Generation of particles can be suppressed, and it can be more stabilized in the quartz glass, and the etching rate can be further reduced. Further, the first element is preferable because it is the element having the least influence in the semiconductor manufacturing process.

本発明の石英ガラスにおいて、前記第１及び第２の元素に加えて、Ａｌが含有された場合、石英ガラス中での電気的安定性は増し、白色異物の発生の抑制により効果的である。   In the quartz glass of the present invention, when Al is contained in addition to the first and second elements, the electrical stability in the quartz glass is increased, which is more effective in suppressing the generation of white foreign matters.

前記第１の元素及びＡｌの総和（Ｍ１＋Ａｌ）と、前記第２の元素の総和（Ｍ２）の配合比が、原子数比率で（Ｍ１＋Ａｌ）／（Ｍ２）＝０．１〜２０、より好ましくは０．２〜１８であると、電気的な安定度がよく、白濁、泡、異物等の発生が少量に抑制される為、好適である。   The compounding ratio of the sum of the first element and Al (M1 + Al) and the sum of the second element (M2) is an atomic ratio of (M1 + Al) / (M2) = 0.1-20, more preferably When it is 0.2 to 18, the electrical stability is good, and the generation of white turbidity, bubbles, foreign matters and the like is suppressed to a small amount, which is preferable.

本発明の石英ガラスを製造する方法は特に限定されないが、２種以上のドープ元素を併せて０．１〜２０質量％、より好ましくは、１．０〜１７質量％含有し、且つ前記ドープ元素として前記第１の元素と第２の元素を含有する混合石英粉を用いて製造する方法が好適である。該混合石英粉は、ドープ元素として前記第１の元素及び第２の元素に加えてＡｌをさらに含むことが好ましい。
前記混合石英粉の平均粒度が０．１〜１００μｍであることが好ましく、１０〜５０μｍがより好ましい。 Although the method for producing the quartz glass of the present invention is not particularly limited, it contains 0.1 to 20% by mass, more preferably 1.0 to 17% by mass of two or more kinds of doping elements, and the doping element A method of manufacturing using mixed quartz powder containing the first element and the second element is preferable. The mixed quartz powder preferably further contains Al as a doping element in addition to the first element and the second element.
The mixed quartz powder preferably has an average particle size of 0.1 to 100 μm, more preferably 10 to 50 μm.

該混合石英粉中の各ドープ元素の配合割合は、ドープ元素の総含有量が０．１〜２０質量％となる範囲内であればよく特に限定されないが、前記第１の元素とＡｌの総和（Ｍ１＋Ａｌ）と第２の元素（Ｍ２）との配合比が原子数比率で、（Ｍ１＋Ａｌ）／（Ｍ２）＝０．１〜２０であることが好ましく、０．２〜１８であることがより好ましい。   The mixing ratio of each dope element in the mixed quartz powder is not particularly limited as long as the total content of the dope element is within a range of 0.1 to 20% by mass, but the sum of the first element and Al is not limited. The compounding ratio of (M1 + Al) and the second element (M2) is an atomic ratio, preferably (M1 + Al) / (M2) = 0.1-20, more preferably 0.2-18. preferable.

該混合石英粉の製造方法は特に限定されないが、例えば、ドープ元素を含む粉体と石英粉とを混合することにより得ることが好適である。前記ドープ元素を含む粉体としては、特に限定されず、ドープ元素からなる単体又はドープ元素を含む化合物の粉体を用いることができる。具体的には、例えば、ＳｉＮ、ＳｉＣ、ＡｌＦ3、Ａｌの酸化物、第２の元素の酸化物等が挙げられる。 The method for producing the mixed quartz powder is not particularly limited. For example, it is preferable to obtain the mixed quartz powder by mixing a powder containing a dope element and quartz powder. The powder containing the doping element is not particularly limited, and a simple substance composed of the doping element or a compound powder containing the doping element can be used. Specifically, for example, SiN, SiC, AlF 3 , an oxide of Al, an oxide of the second element, and the like can be given.

また、前記ドープ元素を含む１種以上の揮発性物質の気体を、水酸基を有する石英粉中に拡散させて、２００〜１１００℃の温度領域で加熱処理し、混合石英粉を得ることができる。前記ドープ元素を含む揮発性物質としては、該ドープ元素を１種以上含む揮発性物質であれば特に限定されないが、例えば、塩化アルミニウム、塩化イットリウム、ヘキサメチルジシラザン、ＳｉＦ4等の揮発性ガスが挙げられる。前記石英粉中に含まれる水酸基の含有量は特に限定されないが、５０〜２００ｐｐｍが好ましい。 Also, mixed quartz powder can be obtained by diffusing a gas of one or more volatile substances containing the doping element into quartz powder having a hydroxyl group, and heat-treating in a temperature range of 200 to 1100 ° C. The volatile substance containing the doping element is not particularly limited as long as it is a volatile substance containing one or more of the doping elements. For example, volatile gases such as aluminum chloride, yttrium chloride, hexamethyldisilazane, SiF 4, etc. Is mentioned. The content of the hydroxyl group contained in the quartz powder is not particularly limited, but is preferably 50 to 200 ppm.

またさらに、前記ドープ元素と石英粉とを含む溶液を乾燥して混合石英粉を作成してもよい。該溶液は、ドープ元素を含む物質を溶媒に混合溶解して作成された溶液と、石英粉とを混合して得られるスラリー溶液が好ましい。前記溶媒としては特に制限はなく、例えば、純水、酸性溶液、塩基性溶液及び有機溶媒等が挙げられる。
前記ドープ元素を含む物質は、１種以上のドープ元素を含み且つ用いる溶媒に溶解される物質であればよく特に限定されず、ドープ元素からなる単体やドープ元素を含む化合物が使用でき、例えば、硝酸アンモニウム、硝酸アルミニウム及び硝酸イットリウム等のドープ元素を含む硝酸塩，シリコーン化合物，弗化アンモニウム，アンモニア，ＳｉＦ4，ドープ元素の酸化物等が挙げられる。 Furthermore, a mixed quartz powder may be prepared by drying a solution containing the dope element and the quartz powder. The solution is preferably a slurry solution obtained by mixing a solution prepared by mixing a substance containing a dope element in a solvent and quartz powder. There is no restriction | limiting in particular as said solvent, For example, a pure water, an acidic solution, a basic solution, an organic solvent etc. are mentioned.
The substance containing the doping element is not particularly limited as long as it contains one or more kinds of doping elements and can be dissolved in the solvent to be used, and a simple substance composed of the doping elements or a compound containing the doping elements can be used. Examples thereof include nitrates containing doping elements such as ammonium nitrate, aluminum nitrate and yttrium nitrate, silicone compounds, ammonium fluoride, ammonia, SiF 4 , oxides of doping elements, and the like.

本発明の石英ガラスの製造方法の第１の例として、石英粉を用いてベルヌイ法により石英ガラスインゴットを作成する方法が挙げられる。該石英粉として前記混合石英粉を用いることが好ましい。石英粉を加熱溶融落下させ、石英ガラスインゴットを作成する際に、該石英ガラスインゴットの表面温度を１８００℃以上、好ましくは１９００〜２１００℃に加熱することが十分な溶融に好適である。   As a first example of the method for producing quartz glass of the present invention, a method of producing a quartz glass ingot by Bernoulli method using quartz powder can be mentioned. The mixed quartz powder is preferably used as the quartz powder. It is suitable for sufficient melting that the surface temperature of the quartz glass ingot is heated to 1800 ° C. or higher, preferably 1900 to 2100 ° C., when the quartz powder is heated and melted and dropped to form a quartz glass ingot.

前記ベルヌイ法が、酸水素火炎を用いるベルヌイ法である場合、加熱雰囲気エリアに供給される水素／酸素の比率が２．５以上であることが好ましく、３．０〜６．０がより好ましい。
また、加熱雰囲気エリアにＮまたはＣを含むガスが供給されることにより、ＮまたはＣを効率的に混合することができる。前記Ｎ又はＣを含むガスとしては、Ｎ2、ＮＨ3、揮発性有機珪素化合物、プロパンガスなどが好適である。 When the Bernoulli method is a Bernoulli method using an oxyhydrogen flame, the hydrogen / oxygen ratio supplied to the heated atmosphere area is preferably 2.5 or more, and more preferably 3.0 to 6.0.
Moreover, N or C can be efficiently mixed by supplying the gas containing N or C to the heating atmosphere area. As the gas containing N or C, N 2 , NH 3 , a volatile organic silicon compound, propane gas and the like are preferable.

本発明の石英ガラスの製造方法において、作成された石英ガラスインゴット中に、泡やクラックが残留している場合、そのインゴットを２ｋｇ／ｃｍ2以上、好ましくは４．０〜１０ｋｇ／ｃｍ2の圧力下の不活性ガス雰囲気中にて１３００℃以上、好ましくは１６００〜１９００℃の温度で加熱成型することにより、インゴット中に残留していた泡及びクラックを減少させることができる。前記不活性ガスとしては、例えば、Ｈｅ、Ｎ2、Ａｒ等が挙げられる。 The method of manufacturing a silica glass of the present invention, the quartz glass ingot was created, if bubbles or cracks remaining, the ingots 2 kg / cm 2 or more, preferably at a pressure of 4.0~10kg / cm 2 Bubbles and cracks remaining in the ingot can be reduced by heat molding in a lower inert gas atmosphere at a temperature of 1300 ° C. or higher, preferably 1600 to 1900 ° C. Examples of the inert gas include He, N 2 , Ar, and the like.

本発明の石英ガラスの製造方法の第２の例として、前記混合石英粉を成型鋳型に詰め、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で、１３００℃以上、好ましくは１６００〜１９００℃に加熱溶融し、石英ガラスインゴットを作成する方法が挙げられる。前記還元性雰囲気としては、例えば、Ｈ2が挙げられる。前記不活性ガスとしては、例えば、Ｈｅ、Ｎ2、Ａｒが挙げられる。
本発明の石英ガラスの製造方法において、加熱溶融時の圧力が、２ｋｇ／ｃｍ2以上、好ましくは、３．０〜６．０ｋｇ／ｃｍ2であると、作成されるインゴット中の泡が少なく、好適である。 As a second example of the method for producing quartz glass of the present invention, the mixed quartz powder is packed in a molding mold, and is 1300 ° C. or higher, preferably 1600 to 1900 ° C. under reduced pressure or in a reducing or inert gas atmosphere. And a method of producing a quartz glass ingot by heating and melting. Examples of the reducing atmosphere include H 2 . Examples of the inert gas include He, N 2 , and Ar.
The method of manufacturing a silica glass of the present invention, pressure at the time of heating and melting is, 2 kg / cm 2 or more, preferably, if it is 3.0~6.0kg / cm 2, less bubbles in the ingot to be created, Is preferred.

本発明の石英ガラスの製造方法の第３の例として、前記混合石英粉を石英管の中に詰め、管内を減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気にして、管外面より１３００℃以上、好ましくは１６００〜１９００℃に加熱溶融し、石英ガラスインゴットを作成する方法が挙げられる。前記還元性雰囲気及び不活性ガスは前述した本発明方法の第２の例と同様である。   As a third example of the method for producing quartz glass of the present invention, the mixed quartz powder is filled in a quartz tube, and the inside of the tube is set to 1300 ° C. or more from the outer surface of the tube under reduced pressure or a reducing or inert gas atmosphere. , Preferably, a method of heating and melting at 1600 to 1900 ° C. to prepare a quartz glass ingot is mentioned. The reducing atmosphere and the inert gas are the same as in the second example of the method of the present invention described above.

本発明の石英ガラスの製造方法の第４の例として、ドープ元素を含む揮発性物質の気体を、水酸基を有する石英多孔質体中に拡散させて、２００℃〜１１００℃の温度領域で加熱処理したのち、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で、１３００℃以上、好ましくは１６００〜１９００℃に加熱溶融して、石英ガラスインゴットを作成する方法が挙げられる。前記水酸基を有する石英多孔質体としては、４塩化珪素を加水分解反応させて作製したスート体、或いはゾルゲル法によって作成した多孔質体などが挙げられる。ドープ元素を含む揮発性物質は前述した例が同様に好適である。   As a fourth example of the method for producing quartz glass of the present invention, a volatile substance gas containing a doping element is diffused into a quartz porous body having a hydroxyl group, and heat treatment is performed in a temperature range of 200 ° C. to 1100 ° C. Then, a method of heating and melting at 1300 ° C. or higher, preferably 1600 to 1900 ° C. under reduced pressure or in a reducing or inert gas atmosphere to prepare a quartz glass ingot. Examples of the quartz porous body having a hydroxyl group include a soot body prepared by hydrolyzing silicon tetrachloride, a porous body prepared by a sol-gel method, and the like. As for the volatile substance containing the doping element, the above-mentioned examples are suitable as well.

本発明の石英ガラスの製造方法の第５の例として、ドープ元素を含む溶液中に、石英多孔質体を漬し、乾燥後、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で、１３００℃以上、好ましくは１６００〜１９００℃の温度で加熱溶融して、石英ガラスインゴットを作成する方法が挙げられる。前記ドープ元素を含む溶液は、ドープ元素からなる単体もしくはドープ元素を含む化合物を混合溶解して作成することが好ましい。   As a fifth example of the method for producing quartz glass of the present invention, a porous porous body is dipped in a solution containing a dope element, dried, and then dried under reduced pressure or in a reducing atmosphere or an inert gas atmosphere. A method for producing a quartz glass ingot by heating and melting at a temperature of not lower than ° C, preferably 1600 to 1900 ° C. The solution containing the doping element is preferably prepared by mixing and dissolving a simple substance composed of the doping element or a compound containing the doping element.

本発明の石英ガラスの製造方法の第６の例として、ドープ元素及び石英粉を含む溶液を乾燥し、多孔質体を作成し、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で１３００℃以上、好ましくは１６００〜１９００℃の温度で加熱溶融して、石英ガラスインゴットを作成する方法が挙げられる。ドープ元素及び石英粉を含む溶液は前述した例が同様に好適である。   As a sixth example of the method for producing quartz glass according to the present invention, a solution containing a dope element and quartz powder is dried to prepare a porous body, and 1300 ° C. under reduced pressure or in a reducing atmosphere or an inert gas atmosphere. As mentioned above, the method of making a quartz glass ingot by heating and melting at a temperature of preferably 1600 to 1900 ° C. is mentioned. As for the solution containing the dope element and the quartz powder, the examples described above are also suitable.

本発明の石英ガラス治具は、表面から少なくとも１ｍｍ深さまでの厚さに本発明の石英ガラスからなるドープ元素含有層を形成したものである。このように本発明の石英ガラスからなる層を形成させることにより、石英ガラス治具としては必要最小限の改良でプラズマ耐食性に優れた治具を得ることができる。なお、本発明の石英ガラス治具において、ドープ元素の含有の態様としては、石英ガラス治具全体にドープされていてもよいが、耐プラズマ性が要求される所定部位にドープ元素含有層を形成させ、他の部分をドープ元素を含まない石英ガラスとすることがコスト削減に有効であり、好ましい。
本発明の石英ガラスからなる層を部分的に形成させる方法は特に限定されないが、例えば、本発明の石英ガラスや混合石英粉を用いて、１）火加工による肉盛溶接処理、２）溶射法、３）コーティング（塗布法）、又は４）貼付け処理等を行うことが好ましい。 The quartz glass jig of the present invention is obtained by forming a doping element-containing layer made of the quartz glass of the present invention to a thickness of at least 1 mm from the surface. By forming the layer made of the quartz glass of the present invention in this way, a quartz glass jig having excellent plasma corrosion resistance can be obtained with the minimum necessary improvements. In addition, in the quartz glass jig of the present invention, the doping element may be contained in the entire quartz glass jig, but a doped element-containing layer is formed at a predetermined site where plasma resistance is required. It is preferable to use quartz glass that does not contain a doping element in the other portions because it is effective for cost reduction.
The method for partially forming the layer made of the quartz glass of the present invention is not particularly limited. For example, using the quartz glass or mixed quartz powder of the present invention, 1) overlay welding by fire processing, 2) thermal spraying method It is preferable to perform 3) coating (coating method) or 4) sticking treatment.

以下に実施例をあげて本発明をさらに具体的に説明するが、これらの実施例は例示的に示されるもので限定的に解釈されるべきでないことはいうまでもない。   The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

（実施例１）
石英粒子９３３ｇ、Ｙ2Ｏ3粉３８ｇ、ＳｉＮ粉１３ｇ及びＳｉＣ粉１７ｇを混合して得た混合石英粉を、酸水素火炎中に、５０ｇ／分の速度で、１ｒｐｍで回転するターゲットインゴット上に溶融落下させ、１００ｍｍφ×６０ｍｍの石英インゴットを作成した。使用するガス条件は、Ｈ2が３００Ｌ／分、Ｏ2が１００Ｌ／分、とした。インゴット成長面の温度は１９５０℃であった。
前記得られたインッゴット内部の泡、異物を光学的目視法で検査したところ、泡と異物の含有量が１００ｃｍ3当りの投影面積で５ｍｍ2であった。また、可視光線の内部透過率が８０％／ｃｍであった。 (Example 1)
A mixed quartz powder obtained by mixing 933 g of quartz particles, 38 g of Y 2 O 3 powder, 13 g of SiN powder and 17 g of SiC powder is placed on a target ingot rotating at 1 rpm at a speed of 50 g / min in an oxyhydrogen flame. A quartz ingot of 100 mmφ × 60 mm was prepared by melting and dropping. The gas conditions used were H 2 of 300 L / min and O 2 of 100 L / min. The temperature of the ingot growth surface was 1950 ° C.
When the bubbles and foreign matters inside the obtained ingot were inspected by an optical visual method, the content of the bubbles and foreign matters was 5 mm 2 in a projected area per 100 cm 3 . Further, the internal transmittance of visible light was 80% / cm.

前記作成されたインゴットを加熱処理炉中にセットして、Ｎ2雰囲気中にて６ｋｇ／ｃｍ2の圧力下で、１８００℃に１時間保持して、２４０ｍｍφ×１０ｍｍ厚に成形した。
得られたガラス成形体からサンプルを切り出し、ガラス体中の元素濃度を蛍光Ｘ線分析で測定したところ、Ｙ：３．０ｗｔ％であった。１０００℃の脱ガス分析から、ＮとＣの含有量を測定した結果、Ｎが５００ｐｐｍ、Ｃが５００ｐｐｍ検知された。 The prepared ingot was set in a heat treatment furnace, held at 1800 ° C. for 1 hour under a pressure of 6 kg / cm 2 in an N 2 atmosphere, and molded into a thickness of 240 mmφ × 10 mm.
When a sample was cut out from the obtained glass molded body and the element concentration in the glass body was measured by fluorescent X-ray analysis, Y was 3.0 wt%. As a result of measuring the contents of N and C from the degassing analysis at 1000 ° C., N was detected at 500 ppm and C was detected at 500 ppm.

また、得られたガラス成形体から外径２２０ｍｍφ×内径１７０ｍｍφ×５ｍｍｔのリング状冶具を切り出し加工した。切り出した冶具の内径部分にシリコンウェーハをセットし、併せてエッチング装置中にセットして、ＣＦ4＋Ｏ2（２０％）のプラズマガスを５０ｓｃｃｍ掛け流し、３０ｔｏｒｒ、１ｋｗ、１００時間のエッチング試験を行った。試験前後の厚さ変化からエッチング速度を算出し、１０ｎｍ／分の結果を得た。 Further, a ring-shaped jig having an outer diameter of 220 mmφ × an inner diameter of 170 mmφ × 5 mmt was cut out from the obtained glass molded body. A silicon wafer is set on the inner diameter portion of the cut out jig, and is set in an etching apparatus. Then, 50 sccm of a CF 4 + O 2 (20%) plasma gas is applied, and an etching test is performed for 30 torr, 1 kW, and 100 hours. It was. The etching rate was calculated from the thickness change before and after the test, and a result of 10 nm / min was obtained.

（実施例２）
石英粒子９４６ｇ、Ａｌ2Ｏ3粉３８ｇ、Ｙ2Ｏ3粉１３ｇ、ＳｉＮ粉１ｇ、ＳｉＣ粉１ｇ及びＡｌＦ3粉１ｇを混合して得た混合石英粉を、酸水素火炎中に、５０ｇ／分の速度で、１ｒｐｍで回転するターゲットインゴット上に溶融落下させ、１００ｍｍφ×６０ｍｍの石英インゴットを作成した。使用するガス条件は、Ｈ2が３００Ｌ／分、Ｏ2が１００Ｌ／分、ＮＨ3が１０Ｌ／分、プロパンガスが１０Ｌ／分、とした。インゴット成長面の温度は１９５０℃であった。 (Example 2)
A mixed quartz powder obtained by mixing 946 g of quartz particles, 38 g of Al 2 O 3 powder, 13 g of Y 2 O 3 powder, 1 g of SiN powder, 1 g of SiC powder and 1 g of AlF 3 powder was placed in an oxyhydrogen flame at 50 g / min. A quartz ingot of 100 mmφ × 60 mm was prepared by melting and dropping onto a target ingot rotating at 1 rpm. The gas conditions used were 300 L / min for H 2 , 100 L / min for O 2 , 10 L / min for NH 3 , and 10 L / min for propane gas. The temperature of the ingot growth surface was 1950 ° C.

作成されたインゴットを実施例１と同様に処理し、評価し、同等の結果を得た。但し、インッゴット内部の泡、異物を光学的目視法で検査したところ、泡と異物の含有量が１００ｃｍ3当りの投影面積で４ｍｍ2であった。また、Ｙ、Ａｌ、Ｎ、Ｃ及びＦについて、得られたガラス成形体からサンプルを切り出し、ガラス体中の元素濃度を蛍光Ｘ線分析で測定したところ、順に、１．０ｗｔ％、２．０ｗｔ％、３００ｐｐｍ、３００ｐｐｍ、３００ｐｐｍであった。 The prepared ingot was processed and evaluated in the same manner as in Example 1, and equivalent results were obtained. However, when the bubbles and foreign matter inside the ingot were inspected by optical visual inspection, the content of the foam and foreign matter was 4 mm 2 in projected area per 100 cm 3 . Moreover, about Y, Al, N, C, and F, when the sample was cut out from the obtained glass molded object and the element density | concentration in a glass body was measured by the fluorescent X ray analysis, it was 1.0 wt% and 2.0 wt in order. %, 300 ppm, 300 ppm, and 300 ppm.

（実施例３）
石英粒子７２１ｇ、Ａｌ2Ｏ3粉２４６ｇ、Ｙ2Ｏ3粉３２ｇ、ＳｉＮ粉１ｇ、ＳｉＣ粉１ｇ及びＡｌＦ3粉１ｇを混合して得た混合石英粉を、酸水素火炎中に、５０ｇ／分の速度で、１ｒｐｍで回転するターゲットインゴット上に溶融落下させ、１００ｍｍφ×６０ｍｍの石英インゴットを作成した。使用するガス条件は、Ｈ2が３００Ｌ／分、Ｏ2が１００Ｌ／分、ＮＨ3が１０Ｌ／分、プロパンガスが１０Ｌ／分、とした。インゴット成長面の温度は１９５０℃であった。 (Example 3)
A mixed quartz powder obtained by mixing 721 g of quartz particles, 246 g of Al 2 O 3 powder, 32 g of Y 2 O 3 powder, 1 g of SiN powder, 1 g of SiC powder, and 1 g of AlF 3 powder was placed in an oxyhydrogen flame at 50 g / min. A quartz ingot of 100 mmφ × 60 mm was prepared by melting and dropping onto a target ingot rotating at 1 rpm. The gas conditions used were 300 L / min for H 2 , 100 L / min for O 2 , 10 L / min for NH 3 , and 10 L / min for propane gas. The temperature of the ingot growth surface was 1950 ° C.

作成されたインゴットを実施例１と同様に処理し、評価し、同等の結果を得た。但し、インッゴット内部の泡、異物を光学的目視法で検査したところ、泡と異物の含有量が１００ｃｍ3当りの投影面積で４ｍｍ2であった。また、Ｙ、Ａｌ、Ｎ、Ｃ及びＦについて、得られたガラス成形体からサンプルを切り出し、ガラス体中の元素濃度を蛍光Ｘ線分析で測定したところ、順に、２．５ｗｔ％、１３．０ｗｔ％、３００ｐｐｍ、３００ｐｐｍ、３００ｐｐｍであった。 The prepared ingot was processed and evaluated in the same manner as in Example 1, and equivalent results were obtained. However, when the bubbles and foreign matter inside the ingot were inspected by optical visual inspection, the content of the foam and foreign matter was 4 mm 2 in projected area per 100 cm 3 . Moreover, about Y, Al, N, C, and F, when the sample was cut out from the obtained glass molded object and the element density | concentration in a glass body was measured by the fluorescent X ray analysis, 2.5 wt%, 13.0 wt was sequentially found. %, 300 ppm, 300 ppm, and 300 ppm.

（実施例４）
石英粒子９６０ｇ、Ａｌ2Ｏ3粉３８ｇ、Ｎｄ2Ｏ3粉１２ｇ、ＳｉＮ粉１ｇ、ＳｉＣ粉１ｇ及びＡｌＦ3粉１ｇを混合して得た混合石英粉を、酸水素火炎中に、５０ｇ／分の速度で、１ｒｐｍで回転するターゲットインゴット上に溶融落下させ、１００ｍｍφ×６０ｍｍの石英インゴットを作成した。使用するガス条件は、Ｈ2が３００Ｌ／分、Ｏ2が１００Ｌ／分、ＮＨ3が１０Ｌ／分、プロパンガスが１０Ｌ／分、とした。インゴット成長面の温度は１９５０℃であった。 Example 4
A mixed quartz powder obtained by mixing 960 g of quartz particles, 38 g of Al 2 O 3 powder, 12 g of Nd 2 O 3 powder, 1 g of SiN powder, 1 g of SiC powder and 1 g of AlF 3 powder was placed in an oxyhydrogen flame at 50 g / min. A quartz ingot of 100 mmφ × 60 mm was prepared by melting and dropping onto a target ingot rotating at 1 rpm. The gas conditions used were 300 L / min for H 2 , 100 L / min for O 2 , 10 L / min for NH 3 , and 10 L / min for propane gas. The temperature of the ingot growth surface was 1950 ° C.

作成されたインゴットを実施例１と同様に処理し、評価し、同等の結果を得た。但し、インッゴット内部の泡、異物を光学的目視法で検査したところ、泡と異物の含有量が１００ｃｍ3当りの投影面積で４ｍｍ2であった。また、Ｎｄ、Ａｌ、Ｎ、Ｃ及びＦについて、得られたガラス成形体からサンプルを切り出し、ガラス体中の元素濃度を蛍光Ｘ線分析で測定したところ、順に、１．０ｗｔ％、２．０ｗｔ％、３００ｐｐｍ、３００ｐｐｍ、３００ｐｐｍであった。 The prepared ingot was processed and evaluated in the same manner as in Example 1, and equivalent results were obtained. However, when the bubbles and foreign matter inside the ingot were inspected by optical visual inspection, the content of the foam and foreign matter was 4 mm 2 in projected area per 100 cm 3 . Further, for Nd, Al, N, C, and F, a sample was cut out from the obtained glass molded body, and the element concentration in the glass body was measured by fluorescent X-ray analysis. %, 300 ppm, 300 ppm, and 300 ppm.

（実施例５）
実施例２と同様の混合石英粉をカーボン鋳型に充填し、１８００℃、Ｎ2ガス中で、４ｋｇ／ｃｍ2の圧力下で加熱溶融し、インゴットを作成し、その後、実施例１と同じ処理を行い、石英ガラス成形体を作成した。実施例２と同様のサンプルを作成し、各評価を行ったところ、実施例２と同様の評価結果が得られた。 (Example 5)
A mixed quartz powder similar to that in Example 2 is filled in a carbon mold, heated and melted at 1800 ° C. in N 2 gas at a pressure of 4 kg / cm 2 to prepare an ingot, and then the same treatment as in Example 1 To produce a quartz glass molded body. Samples similar to those in Example 2 were prepared and evaluated, and the same evaluation results as in Example 2 were obtained.

（実施例６）
実施例２と同様の混合石英粉を、石英管の中に詰めて、管内を減圧に引きながら管外面より１８００℃に加熱溶融してインゴットを作成し、その後実施例１と同じ処理を行い、石英ガラス成形体を作成した。実施例２と同様のサンプルを作成し、各評価を行ったところ、実施例２と同様の評価結果が得られた。 (Example 6)
A mixed quartz powder similar to that of Example 2 is packed in a quartz tube, and the tube is heated and melted to 1800 ° C. from the outer surface of the tube while reducing the pressure in the tube, and then the same treatment as in Example 1 is performed. A quartz glass molded body was prepared. Samples similar to those in Example 2 were prepared and evaluated, and the same evaluation results as in Example 2 were obtained.

（実施例７）
塩化アルミニウム、塩化イットリウム、ヘキサメチルジシラザン、ＳｉＦ4の揮発性ガスを、水酸基を有する石英スート中に拡散させて６００℃で加熱処理した後、１８００℃、Ｎ2ガス中で、４ｋｇ／ｃｍ2の圧力下で加熱溶融してインゴットを作成し、その後、実施例２と同じ処理を行い、石英ガラス成形体を作成した。実施例１と同様のサンプルを作成し、各評価を行ったところ、それぞれ実施例２と同様の評価結果が得られた。 (Example 7)
A volatile gas of aluminum chloride, yttrium chloride, hexamethyldisilazane, and SiF 4 is diffused in a quartz soot having a hydroxyl group and heated at 600 ° C., and then heated at 1800 ° C. in N 2 gas at 4 kg / cm 2. An ingot was prepared by heating and melting under the pressure of, and then the same treatment as in Example 2 was performed to prepare a quartz glass molded body. When the same sample as Example 1 was created and each evaluation was performed, the evaluation result similar to Example 2 was obtained, respectively.

（実施例８）
硝酸アルミニウム、硝酸イットリウム、アンモニア、エチルアルコール、ＳｉＦ4の混合溶解された溶液中に、石英スート体を漬し、乾燥後、１８００℃、Ｎ2ガス中で、４ｋｇ／ｃｍ2の圧力下で加熱溶融した以外は実施例２と同じ処理を行い、石英ガラス成形体を作成した。実施例２と同様のサンプルを作成し、各評価を行ったところ、それぞれ実施例２と同様の評価結果が得られた。 (Example 8)
A quartz soot body is dipped in a mixed solution of aluminum nitrate, yttrium nitrate, ammonia, ethyl alcohol, and SiF 4 , dried, and then heated at 1800 ° C. in N 2 gas at a pressure of 4 kg / cm 2. Except for melting, the same treatment as in Example 2 was performed to prepare a quartz glass molded body. Samples similar to those in Example 2 were prepared and evaluated, and the same evaluation results as in Example 2 were obtained.

（実施例９）
実施例２と各ドープ元素濃度が同等になるように硝酸アルミニウムと硝酸イットリウムと弗化アンモニウムの濃度を調整した水溶液中に、石英粉を混合溶解して作成されたスラリー溶液を乾燥し、得られた多孔質体を、ヘキサメチルジシラザン気体中に置いて、６００℃で１時間処理し、その後、１８００℃、Ｎ2ガス中で、４ｋｇ／ｃｍ2の圧力下で加熱溶融してインゴットを作成し、その後、実施例１と同じ処理を行い、石英ガラス成形体を作成した。実施例２と同様のサンプルを作成し、各評価を行ったところ、実施例２と同様の評価結果が得られた。 Example 9
A slurry solution prepared by mixing and dissolving quartz powder in an aqueous solution in which the concentrations of aluminum nitrate, yttrium nitrate and ammonium fluoride are adjusted so that the concentration of each doping element is the same as in Example 2 is obtained by drying. The porous body was placed in hexamethyldisilazane gas, treated at 600 ° C. for 1 hour, and then heated and melted at 1800 ° C. in N 2 gas at a pressure of 4 kg / cm 2 to produce an ingot. Thereafter, the same treatment as in Example 1 was performed to produce a quartz glass molded body. Samples similar to those in Example 2 were prepared and evaluated, and the same evaluation results as in Example 2 were obtained.

（実施例１０）
塩化アルミニウム、塩化イットリウム、ヘキサメチルジシラザン、ＳｉＦ4の揮発性ガスを、水酸基を有する石英粉中に拡散させて６００℃で加熱処理し、Ｎを３００ｐｐｍ、Ｃを３００ｐｐｍ、Ｆを３００ｐｐｍ、Ａｌを２．０ｗｔ％、Ｙを１．０ｗｔ％含有させた混合石英粉を得た。
得られた混合石英粉を用いて、実施例２、５又は６と同様な方法で石英ガラス体を作成／評価し、実施例２と同等の結果を得た。 (Example 10)
A volatile gas of aluminum chloride, yttrium chloride, hexamethyldisilazane, and SiF 4 is diffused in quartz powder having a hydroxyl group and heat-treated at 600 ° C., and N is 300 ppm, C is 300 ppm, F is 300 ppm, and Al is added. A mixed quartz powder containing 2.0 wt% and 1.0 wt% Y was obtained.
Using the obtained mixed quartz powder, a quartz glass body was prepared / evaluated in the same manner as in Example 2, 5 or 6, and the same result as in Example 2 was obtained.

（実施例１１）
石英粉を、硝酸アルミニウムと硝酸イットリウムと弗化アンモニウムとシリコーン化合物の混合溶液中に溶いて、実施例２と各金属濃度が同等になるようにして作成されたスラリー溶液を乾燥し、Ｎを３００ｐｐｍ、Ｃを３００ｐｐｍ、Ｆを３００ｐｐｍとＡｌを２．０ｗｔ％、Ｙを１．０ｗｔ％含有させた混合石英粉を得た。
得られた混合石英粉を用いて、実施例２、５又は６と同様な方法で石英ガラス体を作成／評価し、実施例２と同等の結果を得た。 (Example 11)
Quartz powder is dissolved in a mixed solution of aluminum nitrate, yttrium nitrate, ammonium fluoride, and a silicone compound, and a slurry solution prepared so that each metal concentration is equivalent to that in Example 2 is dried. A mixed quartz powder containing 300 ppm C, 300 ppm F, 2.0 wt% Al, 1.0 wt% Y was obtained.
Using the obtained mixed quartz powder, a quartz glass body was prepared / evaluated in the same manner as in Example 2, 5 or 6, and the same result as in Example 2 was obtained.

（比較例１）
石英粒子１０００ｇをカーボン鋳型に充填し、真空雰囲気において、１８００℃、１時間の加熱処理を行い、１００ｍｍφ×６０ｍｍの透明ガラス体を作成した。また、実施例１と同様のサンプルを作成し、プラズマエッチングテストを行ったところ、エッチング速度は、１２０ｎｍ／分であった。その他の評価結果は実施例１と同じであった。 (Comparative Example 1)
A carbon mold was filled with 1000 g of quartz particles, and a heat treatment was performed at 1800 ° C. for 1 hour in a vacuum atmosphere to prepare a transparent glass body of 100 mmφ × 60 mm. Moreover, when the same sample as Example 1 was created and the plasma etching test was done, the etching rate was 120 nm / min. The other evaluation results were the same as in Example 1.

（比較例２）
石英粒子９４４ｇ及びＡｌ2Ｏ3粉５６ｇを混合して得た混合石英粉を用いて、実施例１と同様にサンプルを作成し、評価を行った。エッチング速度は、７０ｎｍ／分であった。 (Comparative Example 2)
Samples were prepared and evaluated in the same manner as in Example 1 using mixed quartz powder obtained by mixing 944 g of quartz particles and 56 g of Al 2 O 3 powder. The etching rate was 70 nm / min.

（比較例３）
石英粒子９６２ｇ及びＹ2Ｏ3粉３８ｇを混合して得た混合石英粉を用いて、実施例１と同様にサンプル作成し、評価した。石英ガラス体中には、多数の白濁点（異物）が残った。エッチング速度は、６０ｎｍ／分であった。 (Comparative Example 3)
Samples were prepared and evaluated in the same manner as in Example 1 using mixed quartz powder obtained by mixing 962 g of quartz particles and 38 g of Y 2 O 3 powder. In the quartz glass body, many white cloud points (foreign matter) remained. The etching rate was 60 nm / min.

（比較例４）
石英粒子５４６ｇ、Ａｌ2Ｏ3粉４１６ｇ及びＹ2Ｏ3粉３８ｇを混合して得た混合石英粉を用いた以外は実施例１と同様にして実験を行った。前記混合石英粉中の金属元素濃度は２５質量％、Ａｌ／Ｙの原子数比は２４であった。得られた石英ガラス体中には、多数の泡が残った。エッチング速度は、６０ｎｍ／分であった。 (Comparative Example 4)
An experiment was conducted in the same manner as in Example 1 except that mixed quartz powder obtained by mixing 546 g of quartz particles, 416 g of Al 2 O 3 powder and 38 g of Y 2 O 3 powder was used. The metal element concentration in the mixed quartz powder was 25% by mass, and the atomic ratio of Al / Y was 24. Many bubbles remained in the obtained quartz glass body. The etching rate was 60 nm / min.

Figure 2008056533
Figure 2008056533

Claims (21)

２種以上のドープ元素を併せて０．１〜２０質量％含有する石英ガラスであって、前記ドープ元素が、Ｎ、Ｃ及びＦからなる群から選択される１種以上の第１の元素と、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、ランタノイド及びアクチノイドからなる群から選択される１種以上の第２の元素とを含むことを特徴とする石英ガラス。   A quartz glass containing 0.1 to 20% by mass of two or more doping elements, wherein the doping element is one or more first elements selected from the group consisting of N, C and F; A quartz glass comprising Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, one or more second elements selected from the group consisting of lanthanoids and actinoids. 前記第１の元素の総和（Ｍ１）と、前記第２の元素の総和（Ｍ２）の配合比が、原子数比率で（Ｍ１）／（Ｍ２）＝０．１〜２０であることを特徴とする請求項１記載の石英ガラス。   The compounding ratio of the sum (M1) of the first elements and the sum (M2) of the second elements is an atomic ratio (M1) / (M2) = 0.1-20. The quartz glass according to claim 1. 前記ドープ元素が、さらにＡｌを含むことを特徴とする請求項１記載の石英ガラス。   The quartz glass according to claim 1, wherein the doping element further contains Al. 前記第１の元素及びＡｌの総和（Ｍ１＋Ａｌ）と、前記第２の元素の総和（Ｍ２）の配合比が、原子数比率で（Ｍ１＋Ａｌ）／（Ｍ２）＝０．１〜２０であることを特徴とする請求項３記載の石英ガラス。   The mixing ratio of the sum of the first element and Al (M1 + Al) and the sum of the second element (M2) is (M1 + Al) / (M2) = 0. The quartz glass according to claim 3, wherein 表面から少なくとも１ｍｍ深さまでの厚さに請求項１〜４のいずれか１項記載の石英ガラスからなる層を形成したことを特徴とする石英ガラス治具。   A quartz glass jig comprising the quartz glass layer according to any one of claims 1 to 4 having a thickness of at least 1 mm from the surface. ２種以上のドープ元素を併せて０．１〜２０質量％含有する混合石英粉であって、前記ドープ元素が、Ｎ、Ｃ及びＦからなる群から選択される１種以上の第１の元素と、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、ランタノイド及びアクチノイドからなる群から選択される１種以上の第２の元素とを含むことを特徴とする混合石英粉。   One or more first elements selected from the group consisting of N, C and F, wherein the mixed quartz powder contains 0.1 to 20% by mass of two or more kinds of doping elements. And a mixed quartz powder comprising Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, one or more second elements selected from the group consisting of lanthanoids and actinoids. 前記第１の元素の総和（Ｍ１）と、前記第２の元素の総和（Ｍ２）の配合比が、原子数比率で（Ｍ１）／（Ｍ２）＝０．１〜２０であることを特徴とする請求項６記載の混合石英粉。   The compounding ratio of the sum (M1) of the first elements and the sum (M2) of the second elements is an atomic ratio (M1) / (M2) = 0.1-20. The mixed quartz powder according to claim 6. 前記ドープ元素が、さらにＡｌを含むことを特徴とする請求項６記載の混合石英粉。   The mixed quartz powder according to claim 6, wherein the doping element further contains Al. 前記第１の元素及びＡｌの総和（Ｍ１＋Ａｌ）と、前記第２の元素の総和（Ｍ２）の配合比が、原子数比率で（Ｍ１＋Ａｌ）／（Ｍ２）＝０．１〜２０であることを特徴とする請求項８記載の混合石英粉。   The mixing ratio of the sum of the first element and Al (M1 + Al) and the sum of the second element (M2) is (M1 + Al) / (M2) = 0. The mixed quartz powder according to claim 8, which is characterized by: 前記ドープ元素を各々又は併せて含有する１種又は２種以上の揮発性物質の気体を、水酸基を有する石英粉中に拡散させて、２００℃〜１１００℃の温度領域で加熱処理することを特徴とする請求項６〜９のいずれか１項記載の混合石英粉の製造方法。   A gas of one or more volatile substances each containing the doping element or in combination is diffused in quartz powder having a hydroxyl group, and heat-treated in a temperature range of 200 ° C. to 1100 ° C. A method for producing a mixed quartz powder according to any one of claims 6 to 9. 前記ドープ元素及び石英粉を含む溶液を乾燥することを特徴とする請求項６〜９のいずれか１項記載の混合石英粉の製造方法。   The method for producing mixed quartz powder according to any one of claims 6 to 9, wherein the solution containing the dope element and quartz powder is dried. ベルヌイ法で石英粉からプラズマ耐食性に優れた石英ガラスを作成する方法であって、前記石英粉が請求項６〜９のいずれか１項記載の混合石英粉であり、該混合石英粉を加熱溶融落下させ石英ガラスインゴットを作成する際、該石英ガラスインゴット表面温度を、１８００℃以上に加熱することを特徴とする請求項１〜４のいずれか１項記載の石英ガラスの製造方法。   A method for producing quartz glass having excellent plasma corrosion resistance from quartz powder by the Bernoulli method, wherein the quartz powder is the mixed quartz powder according to any one of claims 6 to 9, and the mixed quartz powder is heated and melted. 5. The method for producing quartz glass according to claim 1, wherein the quartz glass ingot surface temperature is heated to 1800 ° C. or higher when the quartz glass ingot is dropped. 加熱雰囲気エリアに還元性ガスが供給され、供給される水素／酸素の比率が２．５以上であることを特徴とする請求項１２記載の石英ガラスの製造方法。   The method for producing quartz glass according to claim 12, wherein a reducing gas is supplied to the heating atmosphere area, and a ratio of supplied hydrogen / oxygen is 2.5 or more. 加熱雰囲気エリアにＮまたはＣを含むガスが供給されることを特徴とする請求項１２記載の石英ガラスの製造方法。   The method for producing quartz glass according to claim 12, wherein a gas containing N or C is supplied to the heating atmosphere area. 請求項６〜９のいずれか１項記載の混合石英粉を、成型鋳型に詰めて、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で１３００℃以上に加熱溶融して、石英ガラスインゴットを作成することを特徴とする請求項１〜４のいずれか１項記載の石英ガラスの製造方法。   The mixed quartz powder according to any one of claims 6 to 9 is packed in a molding mold and heated and melted to 1300 ° C or higher in a reduced pressure condition or in a reducing atmosphere or an inert gas atmosphere to obtain a quartz glass ingot. It produces, The manufacturing method of the quartz glass of any one of Claims 1-4 characterized by the above-mentioned. 請求項６〜９のいずれか１項記載の混合石英粉を、石英管の中に詰めて、管内を減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気にして、管外面より１３００℃以上に加熱溶融して、石英ガラスインゴットを作成することを特徴とする請求項１〜４のいずれか１項記載の石英ガラスの製造方法。   The mixed quartz powder according to any one of claims 6 to 9 is packed in a quartz tube, and the inside of the tube is heated to 1300 ° C or higher from the outer surface of the tube under reduced pressure or a reducing or inert gas atmosphere. The method for producing quartz glass according to any one of claims 1 to 4, wherein the quartz glass ingot is prepared by melting. 前記ドープ元素を各々又は併せて含有する１種又は２種以上の揮発性物質の気体を、水酸基を有する石英多孔質体に拡散させて、２００℃〜１１００℃の温度領域で加熱処理したのち、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で１３００℃以上に加熱溶融して、石英ガラスインゴットを作成することを特徴とする請求項１〜４のいずれか１項記載の石英ガラスの製造方法。   After diffusing the gas of one or two or more volatile substances each containing the doping element or together into a quartz porous body having a hydroxyl group, heat treatment is performed in a temperature range of 200 ° C. to 1100 ° C., The quartz glass ingot is produced by heating and melting at 1300 ° C or higher in a reduced pressure condition or in a reducing atmosphere or an inert gas atmosphere. Method. 前記ドープ元素を含む溶液中に石英多孔質体を漬し、乾燥後、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で１３００℃以上の温度で加熱溶融して、石英ガラスインゴットを作成することを特徴とする請求項１〜４のいずれか１項記載の石英ガラスの製造方法。   A quartz porous body is immersed in a solution containing the dope element, dried, and then heated and melted at a temperature of 1300 ° C. or higher under reduced pressure or in a reducing atmosphere or an inert gas atmosphere to produce a quartz glass ingot. The manufacturing method of the quartz glass of any one of Claims 1-4 characterized by the above-mentioned. 前記ドープ元素及び石英粉を含む溶液を乾燥し、多孔質体を作成し、減圧条件下又は還元性雰囲気もしくは不活性ガス雰囲気中で１３００℃以上の温度で加熱溶融して、石英ガラスインゴットを作成することを特徴とする請求項１〜４のいずれか１項記載の石英ガラスの製造方法。   The solution containing the dope element and quartz powder is dried to prepare a porous body, and heated and melted at a temperature of 1300 ° C. or higher under reduced pressure or in a reducing or inert gas atmosphere to prepare a quartz glass ingot. The method for producing quartz glass according to any one of claims 1 to 4, wherein: 前記加熱溶融時の圧力が、２ｋｇ／ｃｍ2以上であることを特徴とする請求項１５〜１９のいずれか１項記載の石英ガラスの製造方法。 The method for producing quartz glass according to any one of claims 15 to 19, wherein a pressure at the time of heating and melting is 2 kg / cm 2 or more. 前記作成された石英ガラスインゴットを２ｋｇ／ｃｍ2以上の圧力下の不活性ガス雰囲気中にて１５００℃以上の温度で加熱成型することを特徴とする請求項１２〜２０のいずれか１項記載の石英ガラスの製造方法。 The produced quartz glass ingot is heat-molded at a temperature of 1500 ° C or higher in an inert gas atmosphere under a pressure of 2 kg / cm 2 or higher. A method for producing quartz glass.
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US20080053151A1 (en) 2008-03-06
EP1894896A1 (en) 2008-03-05
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US8156761B2 (en) 2012-04-17
EP1894896B1 (en) 2010-03-31
DE602007005556D1 (en) 2010-05-12

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